Method of making titanium dioxide



Patented Dec. v5, 1939 UNITED STATES PATENT OFFICE 2,182,420. METHOD or MAKING TITANIUM moxma Benjamin Wilson Allan and LRoclie G. Bousquet,

- Baltimore, Md., assignors to American Zirconium Corporation, Baltimore, Md., a corporation of Maryland No Drawing.

7Claims.

sulphate solutions of controlled compositions to give precipitates which on calcination give improved tinting strength. More particularly, it contemplates the use of high concentrations of soluble sulphates other than those of titanium, to give improved precipitates; and it contemplates economies in the present processes of manufacture through the use of these high sulphate concentrations.

Titanium dioxide is made commercially by the hydrolysis of sulphate solutions, obtained by reacting on ilmenite with sulphuric acid, and dissolving the mass in water or dilute acid. These solutions contain both iron and titanium in solution; the ratio of Fe to T102 in the solution is ordinarily about 0.7 to 0.8. In order to get ironfree precipitates, it has been the practice to hydrolize the titanium from solutions containing low Fe concentrationsbetween and 'grams per liter. Dilute solutions of the reaction mass can be employed; but the concentration of titanium dioxide in such event falls to 50 to grams per liter; and the experience of the art is that concentrated solutions of TiOa (from to grams per liter) are necessary to get good pigment properties where the hydrolysis product is essentially titanium hydrate. It has therefore been the practice toreduce the iron content by crystallizing ferrous sulphate from the solution,

or by some other expedient, and adjusting the solution, partially freed from iron, to the desired concentration.

In order to obtain satisfactory yields of pigment, and rapid hydrolysis, it has been necessary to induce hydrolysis by-means of some agent a which renders the solution unstable, for instance by cop'recipitation of alkaline earth sulphate with an alkaline earth base, or by the introduction or formation in situ of colloidal titanium dioxide. These hydrolysis inducers are generally 45 known as seeding agents.

We have discovered that good pigment titanium dioxide may be produced with solutions of titanium containing as low as 100 grams per liter of H02, by increasing the concentration of sol- 50 uble sulphates in solution,

Application February 11, 1935, Serial No. 6,130

We have further discovered that if concentrations. and acidity be properly adjusted, the hydrolysis may take place in the presence of large amounts of iron, without harmful effect on the color of the pigment, and the soluble sulphate 5 present may be essentially ferrous sulphate. It is thus possible 'to hydrolize a purified solution obtained directly from the ilmenite ore, without concentration or removal of iron, merely by adjusting the acid and combined'sulphate concen- 10 trations, and adding a seeding agent. The salt concentration may be adjusted by adding additional ferrous sulphate, or by the addition of any soluble sulphate which will not hydrolize'with' the titanium; and these sulphates may be used 15 to replace ferrous sulphate wholly or in part. Magnesium, tin, aluminum, zinc, sodium, potassium and ammonium sulphates are typical suitable products.

We are aware that salts have hitherto 'Ezen 20 added to titanium sulphate solutions for use in pressure hydrolysis, but these additions were not made to get definite concentrations of salts for given T102 concentrations, to improve the hydrolysis products. as

Many modifications of our process are possible, but three general methods only will be given to enable those skilled in the art to carry out the process in any of its modifications.

A titaniferous ore, preferably ilmenite, ground 30 or unground, is digested with concentrated sulphuric acid in the proportion of one to two parts HzSOi to one part of ore. The resulting dry mass is dissolved in water or titanium and acid a bearing liquor-a by-product of a'subsequentop eration-in the presence of a reducing agent, such as results when metallic iron or zinc is introduced into the dissolving liquor or titanous sulphate crystals are added. The titanium liquor 0 thereby produced, in which all of the iron is inthe ferrous state, which condition is assured by the presence of a small amount of titanous sulphate,

- is then freed of its undissolved solids. The clarification is carried out by settling after coagu- 45 lation of the slimes by means of glue, or by liltration after the addition of diatomaceous earth. or by a combination of the two methods. The clarified titanium solution thus obtained will have an approximate composition somewhere 50 ito within in grams per liter): i

Reduced T102 n 5 F 96-128 .lotal H2304 462-617 Active H2SO4 294-392 Free H2SO4 RA ..per cent' -130 u :g;'about ;,0.8

Total T102 120-166 Note: Active acid=Ti equivalent also. to yield TiOSOi-I-FIGE H2504 F. A.=per cent i'actor of acidity:

Free acid Ti equiv." H X 1 0o Exmrm 1 Treatment of the solution where the factor of acidity of the titanium solution is between To 'a solution preferably within the above range, eitherbefore or after clarification, suflicientbase is added to give a factor .of acidity of about 50%. For this purpose the hydroxide or carbonate of any metal yielding a soluble sul phate such as NazCOa, ZnC0s, MgCOa, etc. can

be used. The following is an analysis of a titanium sulphate solution prepared as above, using sodium carbonate as the alkali (all concentrations in grams per liter):

Total no. 145- Reduced TiOz 7.5 Fe 104.3 NazSm 104.0

Total H2804.- 468 Active H2SO4 285 Free H280 107 F. A per cent '60 Ratio Fe-I-Fe equiv. of Na,so.

TiO

4 Examrm 2 Procedure where the factor of acidity of the titanium solution is between 20% to 70% and the T102 concentration between -155 grams per liter.

Titanium solutions corresponding to the above specifications are prepared from what is known as basic mass, which is prepared by digesting ilmenite with less'sulphuric acid than is necessary to yield titanium disulphate, '1 l(SO4 2. For the purpose of this process it is desirable to obtain a titanium solution with approximately the 191,-.

Total T10 15% Reduced T102 '51)? F TotalHzS .454 Free H280 64 Active H2804 252 A per cent 34 Fc/TiOz ratio .746 S. G. at 44 C 1154 boiled for from flve to six hours-with a recovery of the TiOzpresent of 95% orbetter. The pigment is-washed' free of. impurities and calcined.

In the event that it is desired to use titanium solutions with a lower TiOz concentration than the above, or to improve the tinting strength, use

is made of the addition of FeSO4, NazSO4, or other soluble sulphate, the amount of soluble salt needed depending on the T102 concentration.

EXAMPLE Procedure where the factor of acidity of the titanium solution is between 20-70% and the T102 concentration is above grams per liter.

If extremely high covering 'power is desired from the pigment, the solution such as is pro- I duced by filtration is concentrated, the amount depending on the tinting strength required. Contrary to other processes, we do notremove any of J the ferrous sulphate even when we use concentrated solutions. The addition of soluble sulphates is notnecessary tomaintain high tinting strength, unless there is a deficiency of iron in the original solution; and as the very high T102 concentrations are reached (around 250 grams per.

liter) good results are obtained even at low iron concentrations. v

- To specifically demonstrate the diflerences obtainable by the use of added salts, reference should be had to the following tables:

. Taste I. -E1fect of TiOz concentration, maintaining a uniform low Ffe/TiOz ratio Hydrolysis No 11-1883 11-1880 H 186A H-ISSA Total T101, ./1 J 149.9 172. 5 170 252. 5 Reduced Ti 1 3. 6 4. 3 1. 2 0. 4 Fe a4. a 38.8 37. 1 66 Ratio 227 225 218 .221 Total H280 341. 8 390. 6 360 568 Free H1804... 97. 9 111. 5 87 Active HzSO4 281. 6 322. 5 294. 8 96. 6 F. A., percent. 53. 4 52.8 41. 7 51.6 Percent'TiOa as gel seed 2.0 2. 0 2. 0 2. 0 Percent tinting strength 50 65 I 70 120 All precipitates were calcined under identical con- 1 ditions.

Note that increased T102 concentrations give increased covering. This was known to the prior art; the Fe/TiOa ratio shown in this table is the conventional prior art standard, except that H-188A is much more concentrated than is handled in conventional practice.

Tana: II.Eflect of increasing Fe/TiOz ratios on low TiOz concentration solutions Hydrolysis No H-188B H-150 H-1s90 III-190A H-186E H-lSGG n-isor T102, 149.9 136.8 134.9 129.8 1209 129.4 114 gggiced Ti i 3. 6 1. 8 3. 1 2. 8 l. 3 Present 1. 10 Fa 34.3 90.0 99.9 128.5 mm 34.5 37.

Ratio T .227 .103 .74 .999 Total mso 341. 8 400. 1 454. 9 Free His 97. 9 05. 0 70. 0 Active His 201.0 230.8 229.4 228.3 Other soluble sulphate None None None None 740 MgSOa'IHzO 426 Naisoi Ratio Fe-l-Fe equiv. as soluble sulphate 227 74 999 1 23 1. 57 1 78 20 Note that as the Fe/TiOz ratio. increases, even with decreasing concentrations of T102, the pigment properties are improved. The last two ex v amples show the substitution of other soluble salt for the iron. I 25 TABLE IIL-Efiect 0] increasing Fe/TiOz ratios on medium TiOz concentration solutions Hydrolysis No H-188B H-l82A H-188D H-180B 3-190 H7135];

Total 1 10,. 1 149.9 153.0 158.0 158.3 154.3 115 Reduced Ti 1.-. 3.6 3.5 Present .4 3.56 2.7 F 34. a 102. 0 127. 0 133.7 154. 3 37.1 .227 .672 .803 .844 235 341.8 -481.0 524.3 503.7 97.9 113.4 109.3 75.7 Active also. 281.0 300.5 301 200.1

Other soluble sulphate. .1. i fi. None None None None None 322 ZnSOl Ratio Fe+Fe equ llibafso ub e su p ate 227 7 803 844 1- 0 I 941 53.4 00. 5 01 39 41.4 41.7 2.0 2.0 2.0 2.0 2.0 2.0 90 101 100 105 85 Here also increase in Fe/TiO2 ratio increases tint.

TABLE IV.-Efiect of increasing Fe/TiOz ratios on high TiOz concentration solutions Hydrolysis No H'.186A H-l85D H190C H-1s3B 11. 9 H 183E l. 2 4. 1 4. 25 3. 5 l. 2 Prcsen 31.1 137.3 101 113.4 31.1 91.

350 530 599.8 81 .79 100 Active also. 294. 8 289 30a 8 Other soluble sulphate None None None Ratio Fe+Fe equiv. as soluble sulphate 218 803 L 02 T10: v

F. A., percent. 41.7 37. 7 53 5 Percent 'IiOi as gel seed... 2. 0 2. 0 2. 0 2. 0 2. 0 2. 0 Percent tinting strength p 100 108 110 It will be noted from the above tables that From a production standpoint it is desirable to 60 as the be able to produce a satisfactory hydrolysis prodf drolysis.

ratio decreases the T102 concentration must be The proposed process has certain advantages of commercial value. By its use both the labor and material cost is reduced.

uct from a titanium sulphate solution having the maximum TiOz concentration obtainable without recourse to evaporation. It is commercially practical to produce clarified solutions with a T102 content up to about grams per liter. By the processes now commercially in use such solutions are not suitablevfor preparing TiOz for use as pigment. Y

Boththe dilution to lower the iron concentration and the crystallization followed by evaporation as now practiced in the two principal processes used commercially are expensive. In thev first case, twice the volume of titanium solution has to be used to obtain a given amount of pigment, involving higher handling charges, larger for heating, while in sults with solutions equipment, and

the second case there is to be considered the added cost for steam and power needed for crystallization and concentration, and the titanium losses incurred. Besides overcoming these disadvantages the proposed process effects still greater economies by the use of titanium solution containing an extremely low free acid concentration.

made of the bulk of the F6504 left in the mother liquor. about 70% H2SO4, the FeS04 is precipitated out as the hydrate, copperas. The solids are then removed from the acid, washed with water to remove the adhering acid and used to increase the soluble salt concentration of the titanium solution. The recovered acid is used for digestion of more ore.

As is evident from the examples and tables, our

phate. This is contrary to the teaching" of the priorart, and has resulted for the first time in practical hydrolysis of purified solutions as they are produced in the attack on the ore, without separation of iron, concentration, or dilution.

While low iron-titanium ratios, such as are used by the prior art, give good results with solutions of very high T102 content (200 grams per liter and higher), these ratios give poor reobtainable from ilmenite attack masses without concentration (maximum Ti02 content about 160 grams per liter). The sulphate-titanium ratio should be maintained at fairly high figures for these solutions--a minimum ratio of 0.6 for solutions with a concentration of 160 grams Ti02 per liter is needed to insure good pigment properties. The normal sulphate-titanium ratio in solutions prepared from ilmenite (0.7 to 0.8) gives good results with titanium oxide concentrations of over 150 grams per liter, when used in conjunction with-a hydrolysis inducer. As the T102 concentration is lowered, higher ratios are necessary; and with the lower range of 'Ii02 concentrations (100-110 grams per liter) the sulphate-titanium ratio should be maintained at 1.5 or more. Throughout the entire workable range of H02 concentration, however, increase of the sulphate-titanium ratio will improve the pigment properties, other conditions remaining constant; and for solutions in the high concentration range (above 200 grams per liter) sulphate-titanium ratios of as low as 0.4 give noticeable improvement over the prior art ratios of 0.12 to 0.30.

Our invention is of course, most adapted to hydrolysis of solutions prepared from ilmenite; but substantially iron-free solutions made from rutile, or other titaniferous material, may be improved by our process, by the addition of soluble sulphates. We do not limit ourselves to the examples giv n, which merely illustrate the invention. I

As'is' further indicated by the examples and tables, it is necessary to maintain the factor of acidity o f the solution between 20 and 70%, and moretpreferably between 40 and 50, for optimum resul s.

greater consumption of steam While we have shown titanium gel as a seed- Another feature of this process is that use is- By concentrating the mother liquor to ing agent in all our examples, for the sake of making direct comparisons, we have used other means of inducing hydrolysis with good results, including the formation of colloidal titanium dioxide ln situ. In the claims, the term sulphate-titanium ratio" refers to both the ratio Fe/Tl02', and the ratio Fe+Fe equivalent of soluble sulphate Ti02.

We claim: 1. The method of making titanium dioxide which .comprises digesting ilmenite with sulfuric acid, treating the reaction mass to obtain a clarified solution containing more than 100 grams per liter of 'I i02 and a factor of acidity above 70%, and containing all the sulfate'derived from the ilmenite, adjusting the factor of acidity to from 20%to 70% by adding a substantial amount of a basic compound which forms a soluble sulfate, then hydrolyzing the so-prepared hydrolysis solution, washing and calcining the precipitate.

2. In a process for improving .the pigment properties of titanium dioxide, thacombination of steps comprising substantially increasing the soluble sulfate-TiO2 ratio of a solution of titanium sulfate containing ferrous sulfate without changing the Ti02 concentration, and then hydrolyzingthe so-treated solution by heating at atmospheric pressure.

3. In av process for improving the pigment properties of titanium dioxide the combination of steps comprising adding a sufilcient amount of 'a soluble sulfate to a solution of titanium sulfate containing ferrous sulfate to substantially increase the sulfate-TiOz ratio, without substantially changing the factor of acidity or the H02 concentration of the solution, and then hydrolyzing the so-treated solution by heating at atmospheric pressure. 4

4. The method of making titanium dioxide which comprises digesting ilmenite with sulfuric acid, treating the reaction mass to obtain a clarified solution containing more than 100 grams per liter of Ti02 and all from the ilmenite, substantially increasing the soluble sulfate-TiQz ratio of the solution without of theiron sulfate derived substantially changing the T102 concentration of the solution, then hydrolyzing the so-prepared hydrolysis solution at atmospheric pressure to precipitate T102, and calcining the washed precipitate.

5. The method of making titanium dioxide which comprises digesting ilmenite with sulfuric acid, treating the reaction mass to obtain a clari- .fied solution containing more than grams of T102 per liter and all of-the iron sulfate derived from the ilmenite, adding a water-soluble sulfate to the solution to substantially increase the sulfate-.Ti02 ratio without substantially changing the factor of acidity or the Ti02 concentration of the solution then hydrolyzing the so-prepared hydrolysis solution at atmospheric pressure to precipitate Ti02, and calcining the washed precipitate.

6. The process of acidity of.the hydrolysis solution ismaintained between 20% and'70%.

7. The process of claim 4 in which the soluble sulfate-Ti02 ratio isincreased by the addition of a soluble sulfate of ametal other than iron.

BENJAMIN WILSON AI.L AN. L'ROCHE G. BOUSQUET.

of claim 4 in which the factor 

